WO2013165246A1 - Method and apparatus for the production of urea from ammonia and carbon dioxide - Google Patents
Method and apparatus for the production of urea from ammonia and carbon dioxide Download PDFInfo
- Publication number
- WO2013165246A1 WO2013165246A1 PCT/NL2013/050330 NL2013050330W WO2013165246A1 WO 2013165246 A1 WO2013165246 A1 WO 2013165246A1 NL 2013050330 W NL2013050330 W NL 2013050330W WO 2013165246 A1 WO2013165246 A1 WO 2013165246A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- urea
- condenser
- heat
- medium
- pressure
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
- C07C273/04—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds from carbon dioxide and ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Definitions
- the present invention relates to the field of the production of urea from ammonia and carbon dioxide in a urea plant containing a high-pressure synthesis section.
- the urea plant may comprise a high pressure stripper, a high pressure carbamate condenser and a pool condenser or a pool reactor.
- the steam is used to heat the stripper.
- an object of the present invention to provide an improved method for the production of urea from ammonia and carbon dioxide in a urea plant. More in particular an object of the invention is to provide a method for the production of urea from ammonia and carbon dioxide in a urea plant that operates with reduced energy consumption.
- a method for the production of urea from ammonia and carbon dioxide in a urea plant containing a high- pressure synthesis section with a horizontal pool condenser comprises exchanging heat from a high pressure process medium received in a shell section of the pool condenser to a medium pressure urea containing solution received in a first heat exchanging section provided in the pool condenser to at least decompose ammonium carbamate into NH3 and CO2.
- the method further comprises exchanging heat from the high pressure process medium to a low pressure steam condensate received in a second heat exchanging section provided in the pool condenser to produce low pressure steam.
- a pool condenser is to be understood as a condenser in which the liquid phase is the continuous phase. Such a pool condenser may also be referred to as a submerged condenser.
- high pressure may typically be defined as a pressure above 100 bar (10 MPa), for instance 120 bar (12 MPa).
- Medium pressure may typically be defined as a pressure between 10-35 bar (1-3.5 MPa), for instance between 10-25 bar (1-2.5 MPa)
- intermediate pressure may typically be defined as a pressure between 20-100 bar (2.0-10 MPa), for instance between 25-100 bar (2.5-10 MPa)
- low pressure may be typically defined as a pressure between 2-10 bar (0.2-1 MPa).
- the pool condenser is a shell and tube heat exchanger, wherein the first and second heat exchanging sections each comprise a substantially U-shaped tube bundle.
- the shell and tube heat exchanger may be a submerged condenser that is placed horizontally.
- the shell and tube heat exchanger may comprise a vessel, which vessel is placed substantially horizontally, at least the central axis of the vessel extends substantially horizontally, to be able to perform the method according to the invention.
- Said first and second U-shaped tube bundles extend from the tube sheet of the pool condenser at least partially through an inner space of the pool condenser.
- the second U-shaped tube bundle is configured for the generation of low pressure steam.
- the first U-shaped tube bundle is used for the heat integration with a medium pressure recirculation section.
- the first bundle in use, is filled with a process medium from said medium pressure recirculation section.
- the first bundle is in contact with process medium on the tube side as well as the shell side thereof.
- an oxidizing agent is added to the process for the production of urea to protect the materials of the different parts of the plant against corrosion. By doing so, an oxide skin is formed on the metal surfaces.
- the oxidizing agent may be oxygen, to be added in the form of air or as peroxide, or an oxygen-releasing compound.
- the parts that are in contact with the process medium may be made from an austenitic- ferritic duplex stainless steel grade, which has corrosion resistant properties. In that case, the use of an oxidizing agent may be reduced or even omitted in the process of the production of urea according to the invention.
- the high pressure process medium received in the shell section of the pool condenser is supplied to an after reactor provided downstream of the pool condenser.
- fresh CO2 is fed to the after reactor to provide heat for an endothermic urea reaction inside the after reactor to form a urea synthesis solution.
- the method further comprises feeding gas that is at least produced in the first heat exchanging section to a medium pressure condenser evaporator in which said gas is at least partially, and optionally completely, condensed.
- a medium pressure condenser evaporator in which said gas is at least partially, and optionally completely, condensed.
- the urea/carbamate solution is flashed to an intermediate pressure.
- the resulting liquid is further reduced to medium pressure and heated in the first U-tube bundle of the pool condenser, thereby thus effectively reusing the heat a first time, to decompose the liquid to CO2 and NH3.
- the gas from the separator provided downstream of the first U-shaped tube bundle, is condensed in the shell side of the evaporator.
- the heat of condensation liberated here is substantially used to evaporate water from an aqueous urea solution that is provided to the tube side of the medium pressure condenser evaporator.
- the heat is reused a second time to evaporate water from the urea water mixture on the tube side.
- the water from a urea-water mixture may be evaporated under vacuum conditions in the medium pressure condenser evaporator.
- the medium pressure condenser evaporator is a falling film evaporator.
- efficient counter current operation may be obtained.
- carbamate coming from the low pressure recirculation section may be added via a medium pressure scrubber. By doing so, sufficient temperature difference may be maintained between the shell side and the tube side to obtain the efficient design of the medium pressure condenser evaporator.
- the invention also relates to an apparatus for the production of urea from ammonia and carbon dioxide, preferably using a method according to any one of the preceding claims, wherein the apparatus comprises a high-pressure synthesis section with a horizontal pool condenser configured to receive a high pressure process medium at a shell side thereof, wherein the apparatus comprises a first heat exchanging section for exchanging heat from the high pressure process medium to a medium pressure urea solution received in said first heat exchanging section to decompose ammonium carbamate into N3 ⁇ 4 and CO2, wherein the pool condenser comprises a second heat exchanging section for exchanging heat from the high pressure process medium to a low pressure steam condensate received in said second heat exchanging section to transfer said condensate into low pressure steam.
- the apparatus comprises a high-pressure synthesis section with a horizontal pool condenser configured to receive a high pressure process medium at a shell side thereof, wherein the apparatus comprises a first heat exchanging section for exchanging heat from the high pressure process medium to a
- FIG. 1 shows a schematic diagram of the method for production of urea from ammonia and carbon dioxide according to an embodiment of the invention. Detailed description
- the urea plant comprises an apparatus 1 containing a high-pressure section 2 with a horizontal pool condenser 4, i.e. a so called shell and tube heat exchanger.
- the pool condenser 4 comprises a vessel, which in use, is placed substantially horizontally, with a first heat exchanging section 6 and a second heat exchanging section 8.
- both heat exchanging sections 6, 8 comprise a substantially U-shaped tube bundle 10, 12.
- the first U-shaped tube bundle 10 is configured for condensation of carbamate and for subsequently decomposing of ammonium carbamate into NH3 and CO2 by means of the heat that is released during said condensation.
- the second U-shaped tube bundle 12 is configured to produce low pressure steam. Both U-shaped bundles 10, 12 extend from the tube sheet 16 of the pool condenser 4 at least partly through an inner space defined by the shell 14 of the pool condenser 4.
- the apparatus 1 may further comprise an after reactor, in the shown embodiment a vertical reactor 18, for the final reaction of the urea conversion.
- the after reactor may be combined with the pool condenser.
- the vertical reactor 18 is located at ground level.
- an inlet 19 is provided for supplying fresh CO2 to the reactor to enable the endothermic urea reaction.
- the apparatus 1 may also comprises a CO2 stripper 20 and a medium pressure recirculation system 22.
- the latter system 22 may comprise a separator 24 arranged downstream of the first U-shaped tube bundle 10, a medium pressure rectifying column 26 and a medium pressure condenser evaporator 28.
- the medium pressure condenser evaporator 28 may be a falling film evaporator to enable efficient counter current operation. It was found that an optimal operating pressure of the medium pressure section 22, of the shown embodiment, may be between 15-35 bar (1.5-3.5 MPa), more preferably between 20-30 bar (2-3 MPa). For instance, approximately 22.5 bar (2.25 MPa). In the low pressure section 32 of the apparatus 1 according to the shown embodiment of the invention, this optimal operating pressure may be between 2-7 bar (0.2-0.7 MPa), preferably between 4-6 bar (0.4-0.6 MPa). For instance, approximately 5.8 bar (0.58 MPa). Also the required pressure of steam on the shell of the stripper 20 may be significant lower as compared to the pressure of the prior art method that is described before. This may enable a further decrease of the total energy consumption since the pressure of the turbine extraction steam can be significant lowered.
- the method according to the invention comprises feeding an amount of carbon dioxide to the vertical reactor 18.
- a urea synthesis solution is formed which is supplied (arrow B) to the stripper 20.
- this solution is stripped by the addition of heat and with supplied carbon dioxide as a stripping gas (arrow E).
- a mixed gas stream is obtained that is supplied to the pool condenser 4 (arrow J).
- fresh ammonia is supplied to the pool condenser 4 (arrow K).
- the urea solution that is formed in the vessel of the pool condenser 4 is supplied to the vertical reactor 18 (arrow L).
- the synthesis pressure is kept at an operating level of between 125-175 bar (12.5-17.5 MPa), more preferably between 140- 150 bar (14-15 MPa). For instance, approximately 144 bar (1.44 MPa).
- the separator 24 is arranged downstream the first U-shaped tube bundle 10 and separates the gas phase and the liquid phase from said tube bundle 10.
- an intermediate flash tank 30 is provided that may supply CO2 rich gas to the medium pressure rectifying column 26 (arrow C) to correct the NH3/CO2 ratio of the liquid from the first U-shaped tube bundle 10.
- the operating pressure used in the intermediate flash tank may be for instance between 20-80 (2-8 MPa), more preferably between 30 and 70 bar (3-7 MPa), even more preferably between 50-60 bar (5-6 MPa), for instance 55 bar (5.5 MPa).
- the liquid is discharged to the low pressure recirculation section 32 (arrow D).
- the gas from the medium pressure rectifying column 26, the gas from the separator 24 and gas from the synthesis (arrow F) are combined and condensed in the shell side of the medium pressure condenser evaporator 28. Consequently, the heat is effectively reused a second time to evaporate water from the urea melt solution on the tube side.
- recirculation system 22 may further comprise a medium pressure scrubber 34. Somewhere along the condensation trajectory, for instance halfway said trajectory, carbamate coming from the low pressure recirculation section 32 is added to the medium pressure condenser evaporator 28 (shell-side) via the medium pressure scrubber 34. By doing so, sufficient temperature difference is maintained between the shell and tube side of the medium pressure condenser evaporator 28 resulting in an efficient heat exchanger design.
- the concentrated carbamate solution coming from the shell side of the medium pressure condenser evaporator 28 is supplied to the pool condenser 4 (arrow G) using a high pressure carbamate pump 36.
- the uncondensed gases together with the inerts are scrubbed in the medium pressure scrubber 34 using the carbamate coming from the low pressure recirculation section 32 (arrow H).
- the resulting gas is supplied to the low pressure absorber 38 (arrow I).
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heat-Exchange Devices With Radiators And Conduit Assemblies (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Priority Applications (13)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MX2014013381A MX364219B (es) | 2012-05-03 | 2013-05-02 | Metodo y aparato para la produccion de urea a partir de amoniaco y dioxido de carbono. |
PL17151200T PL3190101T3 (pl) | 2012-05-03 | 2013-05-02 | Sposób i urządzenie do produkcji mocznika z amoniaku i dwutlenku węgla |
EA201401207A EA030380B1 (ru) | 2012-05-03 | 2013-05-02 | Способ и установка для производства мочевины из аммиака и диоксида углерода |
BR112014026866-5A BR112014026866B1 (pt) | 2012-05-03 | 2013-05-02 | Processo e aparelho para a produção de ureia a partir de amônia e dióxido de carbono |
EP13724002.4A EP2844641B1 (en) | 2012-05-03 | 2013-05-02 | Method and apparatus for the production of urea from ammonia and carbon dioxide |
CN201380023327.4A CN104321305B (zh) | 2012-05-03 | 2013-05-02 | 由氨和二氧化碳制备尿素的方法和装置 |
US14/398,425 US9505712B2 (en) | 2012-05-03 | 2013-05-02 | Method and apparatus for the production of urea from ammonia and carbon dioxide |
JP2015510204A JP6541570B2 (ja) | 2012-05-03 | 2013-05-02 | アンモニア及び二酸化炭素から尿素を製造するための方法、並びに装置 |
CA2871724A CA2871724C (en) | 2012-05-03 | 2013-05-02 | Method and apparatus for the production of urea from ammonia and carbon dioxide |
AU2013257378A AU2013257378B2 (en) | 2012-05-03 | 2013-05-02 | Method and apparatus for the production of urea from ammonia and carbon dioxide |
AP2014008082A AP3891A (en) | 2012-05-03 | 2013-05-02 | Method and apparatus for the production of urea from ammonia and carbon dioxide |
EP17151200.7A EP3190101B1 (en) | 2012-05-03 | 2013-05-02 | Method and apparatus for the production of urea from ammonia and carbon dioxide |
MYPI2014703218A MY190234A (en) | 2012-05-03 | 2013-05-02 | Method and apparatus for the production of urea from ammonia and carbon dioxide |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12166579 | 2012-05-03 | ||
EP12166579.8 | 2012-05-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013165246A1 true WO2013165246A1 (en) | 2013-11-07 |
Family
ID=48468720
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/NL2013/050330 WO2013165246A1 (en) | 2012-05-03 | 2013-05-02 | Method and apparatus for the production of urea from ammonia and carbon dioxide |
Country Status (15)
Country | Link |
---|---|
US (1) | US9505712B2 (zh) |
EP (2) | EP3190101B1 (zh) |
JP (2) | JP6541570B2 (zh) |
CN (1) | CN104321305B (zh) |
AP (1) | AP3891A (zh) |
AU (1) | AU2013257378B2 (zh) |
BR (1) | BR112014026866B1 (zh) |
CA (1) | CA2871724C (zh) |
EA (2) | EA034717B1 (zh) |
HR (1) | HRP20191820T1 (zh) |
MX (1) | MX364219B (zh) |
MY (1) | MY190234A (zh) |
PE (1) | PE20142379A1 (zh) |
PL (1) | PL3190101T3 (zh) |
WO (1) | WO2013165246A1 (zh) |
Cited By (8)
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WO2016085343A1 (en) * | 2014-11-27 | 2016-06-02 | Stamicarbon B.V. | Method and plant for producing urea-ammonium nitrate (uan) |
WO2020183717A1 (en) | 2019-03-14 | 2020-09-17 | Toyo Engineering Corporation | Process and apparatus for urea production |
EP3619194B1 (en) | 2017-05-05 | 2021-03-03 | Casale SA | Process and plant for the synthesis of urea |
EP3296676B1 (de) | 2016-09-16 | 2021-06-30 | thyssenkrupp Industrial Solutions AG | Anordnung und verfahren zur kondensation eines heissen sauren gemischs |
US11332437B2 (en) | 2019-12-30 | 2022-05-17 | Stamicarbon B.V. | Urea production with multiple evaporators |
US11420937B2 (en) | 2019-12-30 | 2022-08-23 | Stamicarbon B.V. | Urea plant with chilled condensation section |
WO2022177438A1 (en) * | 2021-02-22 | 2022-08-25 | Stamicarbon B.V. | Urea production process and plant with parallel mp units |
US11905234B2 (en) | 2019-12-30 | 2024-02-20 | Stamicarbon B.V. | Ammonia removal from urea finishing |
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US10135831B2 (en) | 2011-01-28 | 2018-11-20 | F5 Networks, Inc. | System and method for combining an access control system with a traffic management system |
US10015143B1 (en) | 2014-06-05 | 2018-07-03 | F5 Networks, Inc. | Methods for securing one or more license entitlement grants and devices thereof |
US10505818B1 (en) | 2015-05-05 | 2019-12-10 | F5 Networks. Inc. | Methods for analyzing and load balancing based on server health and devices thereof |
CA2997366A1 (en) * | 2015-09-08 | 2017-03-16 | Toyo Engineering Corporation | Urea manufacturing method and urea manufacturing apparatus |
US10972453B1 (en) | 2017-05-03 | 2021-04-06 | F5 Networks, Inc. | Methods for token refreshment based on single sign-on (SSO) for federated identity environments and devices thereof |
KR102564759B1 (ko) | 2017-10-27 | 2023-08-07 | 스태미카본 비.브이. | 고압 카바메이트 응축기 |
CA3124342C (en) * | 2018-12-21 | 2023-01-03 | Stamicarbon B.V. | Urea production process and plant with heat integration in low pressure recovery section |
JP7157684B2 (ja) | 2019-03-14 | 2022-10-20 | 東洋エンジニアリング株式会社 | 尿素製造方法および装置 |
EP3736415A1 (en) * | 2019-05-10 | 2020-11-11 | Yara International ASA | Steam network assembly for a plant comprising an ammonia-producing unit and a urea-producing unit |
EP4330227A1 (en) | 2021-04-28 | 2024-03-06 | Stamicarbon B.V. | Chemical reactor with internal static mixers |
CA3222982A1 (en) | 2021-06-11 | 2022-12-15 | Stamicarbon B.V. | Urea production with triple mp streams |
WO2023158314A1 (en) | 2022-02-21 | 2023-08-24 | Stamicarbon B.V. | Low biuret urea production |
CN114681950B (zh) * | 2022-03-21 | 2023-02-10 | 三江化工有限公司 | 一种甲基叔丁基醚mtbe装置中甲醇回收塔*** |
WO2023219506A1 (en) | 2022-05-13 | 2023-11-16 | Stamicarbon B.V. | High pressure carbamate condensation apparatus |
WO2024112198A1 (en) | 2022-11-22 | 2024-05-30 | Stamicarbon B.V. | Urea melamine plant with melamine off-gas condenser |
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WO2009141344A1 (en) | 2008-05-19 | 2009-11-26 | Dsm Ip Assets Bv | Process for the production of urea from ammonia and carbon dioxide |
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2013
- 2013-05-02 MY MYPI2014703218A patent/MY190234A/en unknown
- 2013-05-02 EA EA201890472A patent/EA034717B1/ru not_active IP Right Cessation
- 2013-05-02 BR BR112014026866-5A patent/BR112014026866B1/pt active IP Right Grant
- 2013-05-02 PE PE2014001916A patent/PE20142379A1/es active IP Right Grant
- 2013-05-02 WO PCT/NL2013/050330 patent/WO2013165246A1/en active Application Filing
- 2013-05-02 JP JP2015510204A patent/JP6541570B2/ja active Active
- 2013-05-02 EP EP17151200.7A patent/EP3190101B1/en active Active
- 2013-05-02 CA CA2871724A patent/CA2871724C/en active Active
- 2013-05-02 AP AP2014008082A patent/AP3891A/en active
- 2013-05-02 MX MX2014013381A patent/MX364219B/es active IP Right Grant
- 2013-05-02 EA EA201401207A patent/EA030380B1/ru not_active IP Right Cessation
- 2013-05-02 CN CN201380023327.4A patent/CN104321305B/zh active Active
- 2013-05-02 EP EP13724002.4A patent/EP2844641B1/en active Active
- 2013-05-02 PL PL17151200T patent/PL3190101T3/pl unknown
- 2013-05-02 AU AU2013257378A patent/AU2013257378B2/en active Active
- 2013-05-02 US US14/398,425 patent/US9505712B2/en active Active
-
2018
- 2018-02-05 JP JP2018018025A patent/JP6596522B2/ja active Active
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2019
- 2019-10-07 HR HRP20191820TT patent/HRP20191820T1/hr unknown
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See also references of EP2844641A1 |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016085343A1 (en) * | 2014-11-27 | 2016-06-02 | Stamicarbon B.V. | Method and plant for producing urea-ammonium nitrate (uan) |
CN107108382A (zh) * | 2014-11-27 | 2017-08-29 | 斯塔米卡邦有限公司 | 生产尿素硝酸铵(uan)的方法和装置 |
US10315925B2 (en) | 2014-11-27 | 2019-06-11 | Stamicarbon B.V. | Method and plant for producing urea-ammonium nitrate (UAN) |
EA033176B1 (ru) * | 2014-11-27 | 2019-09-30 | Стамикарбон Б.В. | Способ и установка для производства карбамидоаммониевого нитрата (uan) |
EP3296676B1 (de) | 2016-09-16 | 2021-06-30 | thyssenkrupp Industrial Solutions AG | Anordnung und verfahren zur kondensation eines heissen sauren gemischs |
EP3619194B1 (en) | 2017-05-05 | 2021-03-03 | Casale SA | Process and plant for the synthesis of urea |
US11279671B2 (en) | 2017-05-05 | 2022-03-22 | Casale Sa | Process and plant for the synthesis of urea |
WO2020183717A1 (en) | 2019-03-14 | 2020-09-17 | Toyo Engineering Corporation | Process and apparatus for urea production |
US11332437B2 (en) | 2019-12-30 | 2022-05-17 | Stamicarbon B.V. | Urea production with multiple evaporators |
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BR112014026866A2 (pt) | 2017-06-27 |
CA2871724C (en) | 2019-08-27 |
EA201890472A2 (ru) | 2018-07-31 |
EP2844641A1 (en) | 2015-03-11 |
AU2013257378B2 (en) | 2017-03-09 |
EP3190101B1 (en) | 2019-09-25 |
CN104321305B (zh) | 2017-03-01 |
US20150119603A1 (en) | 2015-04-30 |
EA201401207A1 (ru) | 2015-07-30 |
CN104321305A (zh) | 2015-01-28 |
US9505712B2 (en) | 2016-11-29 |
JP6541570B2 (ja) | 2019-07-10 |
PL3190101T3 (pl) | 2020-03-31 |
CA2871724A1 (en) | 2013-11-07 |
JP2015519327A (ja) | 2015-07-09 |
MX364219B (es) | 2019-04-16 |
AP3891A (en) | 2016-11-10 |
AP2014008082A0 (en) | 2014-11-30 |
JP2018076379A (ja) | 2018-05-17 |
HRP20191820T1 (hr) | 2020-01-24 |
EA034717B1 (ru) | 2020-03-12 |
EP2844641B1 (en) | 2017-01-18 |
JP6596522B2 (ja) | 2019-10-23 |
AU2013257378A1 (en) | 2014-11-13 |
PE20142379A1 (es) | 2015-01-25 |
MY190234A (en) | 2022-04-06 |
MX2014013381A (es) | 2015-09-08 |
EA201890472A3 (ru) | 2018-11-30 |
EP3190101A1 (en) | 2017-07-12 |
EA030380B1 (ru) | 2018-07-31 |
BR112014026866B1 (pt) | 2020-09-24 |
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